Plastic composition



Unite PLASTIC COMPOSITION No Drawing. Application March 17, 1955 Serial No. 495,035

10 Claims. (Cl. 106-383) This invention relates to a new composition of matter having sufiicient plasticity to be molded or trowelled into various shapes and structures which may be hardened by rying or baking to form useful structures and articles. it also relates to new articles and structures prepared from such compositions of matter. In its broad applications, this invention relates to new plastic compositions which, when molded and dried, baked, or fired, produce structures and articles having a highly refractive character. in certain specific aspects, the compositions can be molded and dried, baked, or fired to produce articles or structures having a relatively high heat transmission capacity.

it has long been desired to have a plastic substance that can be poured, molded, or trowelled into shapes and structures which can be hardened by drying or baking to form an eflicient, solid heat transfer material.

It is frequently desired to maintain process fluids contained in pipelines, valves, or other containers at an elevated temperature to prevent crystallization, polymerization, objectionable lowering of viscosity, or freezing. This is most commonly done by providing the fluid containers with jackets containing vapors or liquids maintained at a desired elevated temperature. Such jacketing is very expensive and can not always be readily available. A low-cost alternate to jacketing comprises the wrapping or laying of tubing around or adjacent to the container to which it is desired to transfer heat, and passing a heating medium through such tubing. The positioning of heating tubes adjacent to a container or pipeline is referred to as tracing. Tracing is quite readily installed but its effectiveness is very limited by reason of poor contact between the tracing and the object to be heated.

Attempts have been made to provide a plastic composition which, when applied over the installed tracing States Patent "ice 2 shaped into metal casting molds and crucibles which after baking or firing have a relatively high refractiveness so that even high melting metals such as titanium can be cast into relatively smooth-surfaced, useful shapes and articles.

It is an object of this invention to provide new compositions of matter.

It is another object of this invention to provide new and useful structures and articles composed of a new composition of matter.

It is still another object of this invention to provide a new and improved composition of matter which may be readily molded, trowelled, or poured into various shapes or structures which may be hardened by drying or baking to form useful structures and articles having a highly refractory character.

It is a further object of this invention to provide an improved composition of matter which may be readily as a putty or plaster and dried, will improve the heat transmission from the tracing to the heated container. Finely divided metals, ceramic aggregates like silicon carbide, and graphite have been mixed with plastic substances or binders such as clay, resin, sodium silicate, and the like and a liquid vehicle, and this plastic medium packed or trowelled over the tracing positioned on the object to be heated.

The plastic compositions heretoforeused for this purpose have been found to be deficient in several respects. in some cases, the adhesion was poor so that the dried material crumbled and cracked off in use. the material had a high degree of alkalinity and was objectionably toxic and corrosive. The metal powders were often oxidized with the result that the heat transmission characteristics were low, or a large quantity of plastic substance or binder was needed to hold the mass in place. plied because of extreme stickiness.

' It has also been heretofore desired to have a plastic In other cases, the mass was not easily ap- In some cases, i

composition that can be readily molded or otherwise applied over a traced container and dried to form a tightly adhering solid having a high heat transmission capacity.

Other objects of this invention will appear hereinafter.

The objects of this invention may be accomplished, in general, by forming a mixture of a finely divided refractory material, a liquid vehicle that will be evaporated or volatilized'from the mixture by heating, and a sodium oxyfluoborate. The mixture may be formed or shaped into a structure or article, or may be applied over a traced container, and then dried, baked, or fired to form useful structures or articles as will appear more in detail hereinafter.

Sodium oxyfluoborate is a compound described and claimed in copending application of Norval D. Clare and Alden I. Deyrup, Serial No. 469,024, filed November 15, 1954, now abandoned and replaced by continuation-inpart application Serial No. 585,153, filed May 16, 1956. As stated in that application, sodium fluoride and boric oxide form a definite addition compound of the formula The physical properties of the hydrate are similar .to those of the anhydrous compound except that it begins to soften at a lower temperature. Sodium oxyfluoborate may be obtained by mixing dry powders of sodium fluoride and boric acid in the correct stoichiometric quantities and heating the mixture under reflux at ambient pressure with stirring. The pentahydrate of sodium oxyfluoborate can readily be obtained by evaporating the 77% solution to dryness at around -110 C. The anhydrous material can be obtained from the hydrate by heatingthe latter for an hour or two at around 650 C. In addition to the definite sodium oxyfluoborate or sodium oxyfluoborate hydrate discussed above, i. e., as represented by the formulae 4NaF-5B O and 4NaF- 513203 solid sodium fluoride reacts directly with solid boric acid to form initially clear aqueous solutions when the mole ratio of the mixture of the reactants, and hence of the product, within the somewhat approximate V NaFZB203 limits of between about 4:4.68 and 4:5.80.

It has now been found that sodium oxyfluoborate is particularly desirable for use as a binder or cement with a finely divded refractory material, for example, metal or graphite particles, or particles of alumina, xirconia, zircon, chromia, titania, magnesia, silica, beryllia, or the like, to produce a composition which, when moistened with any liquid that is substantially inert to Fthe other ingredients, for example, water, liquid hydrocarbon, turpentine, pine oil, vegetable and animal oils, or organic liquids, preferably organc liquids of relatively low volatility, can be molded, poured, or trowe'lled into shapes and articles which, when hardened by drying or baking, will have a highly refractory character. sired toproduce a composition that will'have arelatively high heat transmission capacity, it willbe necessary to use-finely divided metal or graphite as the refractory material; Although metal powders such as copper, aluminum or iron powders can be'used .inpro'ducing a useful composition having good heat transmission characteristics, finely divided graphite has given much superior results as an efficient heat-transmittingproduct; .Not only from a standpoint of heat transmission, but because of better adhesion, easier handling, and lighter weight. The sodium oxyfiuob-orate .to be used :in' the mixture maybe the anhydrous material represented by the formula N aF:B in which the mole ratio of NaF to' B 0 may vary between 4:4.68 and 4:5180, 'oruit may be the penta'hydrate of such sodium oxyfluoborate, e. g., a composition in the range of 4NaF-4.68B O -5H O to 4NaF-5;8'0B 0 -5H O The particle size of the refractory material used is .not critical, particle sizes from 20m 400 mesh being usable. Preferably, a mixture of fine and coarse sizes of particles are used to obtain the best results. For example, a mixture of coarse particles'between 20 and 80 mesh with fine particles of 100 to 400 mesh will produce a highly desirable composition when the fineiparticles are present in about double the amount of the coarse particles. a

When thehydrate is used in mixtures with graphite, the

proportions of sodium oxyfluoborate hydrate'to graphite should be Within the ranges of between 4% and 50% by weight of the oxyfluoborate to between 50%' and 96% by Weight of finely divided graphite' When using the anhydrous oxyfiuobor'ate proportionately, less may beused.

Somewhat improved results may be obtained by the addition to the aforesaid mixture of a plas'ticizing agent such as a plastic clay, Structures'and articles having particularly desirable heat transmission characteristics havebeen obtained by the use of graphiteand sodium oxyfiuoborate compositions containing clays of thebentonitic or 'rnontmorillonite type.

Whenusingmixtures of sodium 'oxyfluoborate hydrate withgraphite and day, the proportions of constituents should be in the approximate ranges of 4% to 50% by weight of sodium oxyfluoborate hydrate, 35% to 95.99% by weight of graphite, and

.01% to 15%,by weight of clay.

When it is demixture is to be used for molding or trowelling, a mass having the consistency of plaster or putty is usually preferred. When the mixture is to be used in a casting or pouring operation in'a for m or mold, it may be most desirable to have the mass in the consistency of thick cream or grouting cement.

in using the plastic mixture for covering a traced object such as a traced pipeline, valve, or other container, it is usually prefered to plaster and trowel the mixture over the traced-object so as to uniformly cover the tracing to a inches. v

The object, covered with the plastic mixture, may then be dried either under atmospheric conditions or by applied heat. Temperatures of from 100 ;C. to 1000 C. 7

may be used for this purpose of drying or baking.

If desired, the object having the dried or baked covering of the heat transmission material of this invention may be covered with a thermal insulation such as asbestos, 85% magnesia, cork, ,orsimilar material in a known manner.

. Although :the ,cornposition'or" thisinvention-when prepared with .a heat conductive refractory material has a desirable utility as a heat conductive covering on traced objects, it has many :other ;uses as .above indicated. I have discovered that these compositions, as wellas ,compositions comprising .non-theat conducting refractory materials, have outstandingutility for forming molds ,for

the "casting'of metal, ;e. g.,.iron, steel, nickel, copper, etc., into desirable forms and shapes. Preliminary trials have shown that molds or cruciblesshaped from .such compositions and hardened by baking are surprisingly of especial utility-for the casting'of shaped articles from molten titanium. Heretofore, nofsatisfactory material was'known that couldbe formed into a mold" or crucible for the casting-of articles from molten titanium.

The followingexample discloses a preferred .com- 1 position and process for-the production of metal casting When the clay to be 'used is bentonite, the optimum amount in the composition will be 'between'about .0l%

, and 2% by weight of the composition.

When it is desired to -substitute a metal powder or other refractory material for graphite in the abovementioned exemplary compositions, it may be used volme for volumein place of the graphite.

'In prepaflng'the plastic composition, it'is preferred to add an aqueous solution of sodium oxyfluoborateto an aqueous disperlsion'of bentoniteor other plastic clay and the refractrymaterial added to the aqueous mixture; however, useful compositions can be made by mixing of the ingredients in anyother order. The amount of water or. other liquid yehicle used in the mixture will depend uponthe. desired consistency of the'mixture, When the molds or-crucibles: V a V A 50% solution of sodium oxyfluoborate hydrate (4NaF -5B O -5H O) is prepared by dissolvingl83 grams of the same in 183 grams of water. -A bentonite suspension is prepared by'blending 4 grams of a swelling type of bentoniticwclay with 36 grams of w'ater. Ihe bentonite suspension is thoroughly mixed with the solution of sodium 'oxyfluoborate for use as the liquid binder of the molding composition. A blend of graphite powders is then prepared'using 240 gramsof 20+60 meshsize, 240 grams of 60+100 mesh size, and 120 vgrams of --l00-|-200 mesh size for a total weightof 600.grams. V

The solution containing the bentonite is then thoroughly mixed with thergraphite powder mixture to.form a'moldable'composition. This material is then pressed around a pattern to make a metal casting moldorrformed into any desirable shape such as a crucible .(using a crucible'mold). The shapes-are slowly dried at gradually increasing temperatures'up through C; and then duce'a consistency suitablefor making metal moldsiin accordance with conventional foundrypractice. :The

shaped-articles are then baked at.200 --'-.400IC.;to; re move the 'liquidvehicle(linseed-oil). Agceramicibond is developed by :heatingtheobjects on up to temperatures in the range of 700-l000 "C. The sodium oxyfluoborate powder fuses at-these temperatures to 'develop a strong vitreous bond in this composition. Porosity .of

depth of one-eighth inch to one or more the mixture can be controlled by varying the particle size distribution of the graphite aggregate. Other refractory materials, e. g., alumina, zirconia, chromia, or magnesia, can be substituted for the graphite to produce metal mold compositions.

Since it is obvious that many changes and modifications can be made in the above-described details without departing from the nature and spirit of the invention, it is to be understood that the invention is not to be limited to said details except as set forth in the appended claims.

I claim:

1. A mixture composed essentially of 4% to 50% by weight of a substance from the group consisting of NaF:B O and NaF:B O -5H O in which the mole ratio of NaF to B varies between 4:468 and 4:5.80, and 50% to 96% by weight or" a finely divided heat conductive refractory material, with sufiicient added water to induce in the mixture the desired plasticity.

2. The mixture of claim 1 in which the refractory material is graphite.

3. A mixture composed essentially of 4% to 50% by weight or a substance from the group consisting of NaF:B O and NaF:B O -5H O in which the mole ratio of NaF to B 0 varies between 4:4.68 and 425.80, 35% to 95.99% by weight of a finely divided heat conductive refractory material, and 0.01% to 15% by weight of clay, with sufiicient added water to induce in the mixture the desired plasticity.

4. The mixture of claim 3 in which the refractory material is graphite.

5. The mixture of claim 3 in which the refractory material is graphite and the clay is bentonite.

6. A traced container covered with a solid heat transfer composition composed essentially of 4% to 50% by weight of a substance from the group consisting of NaF:B O and NaFzB O -fiH o in Which the mole ratio of N21? to B 6 varies between 424.68 and 4:5.80, and 50% to 96% by weight of a finely divided heat conductive refractory material.

7. A traced container as defined in claim 6 in which the refractory material is graphite.

8. A traced container covered with a solid heat transfer composition composed essentially of 4% to 50% by weight of a substance from the group consisting of NaF:B O and NaRB OySI-I O in which the mole ratio or NaF to B 0 varies between 4:4.68 and 415.80, to 95.99% by weight of a finely divided heat conductive refractory material, and 0.01% to 15% by Weight of clay.

9. A traced container as defined in claim 8 in which the refractory material is graphite.

10. A traced container as defined in claim 8 in which the refractory material is graphite and the clay is bentonite.

References Cited in the file of this patent UNITED STATES PATENTS 1,886,252 Gann et a1 Nov. 1, 1932 1,917,759 Gann July 11, 1933 2,196,971 Boughton Apr. 16, 1940 2,201,366 Grodsky May 21, 1940 2,753,608 Nolan July 10, 1956 OTHER REFERENCES Ryss et al.: Equilibrium in the System Sodium Fluoride-Boric Acid, J. Applied Chem., U. S. S. R., Eng. Trans. 25, pp. 157-161 (1952), No. 2, February. 

1. A MIXTURE COMPOSED ESSENTIALLY OF 4% TO 50% BY WEIGHT OF A SUBSTANCE FROM THE GROUP CONSISTING OF NAF:B2O3 AND NAF:B2O3 5H2O IN WHICH THE MOLE RATIO OF NAF TO B2O3 VARIES BETWEEN 4:4.68 AND 4:5.80, AND 50% TO 96% BY WEIGHT OF A FINELY DIVIDED HEAT CONDUCTIVE REFRACTORY MATERIAL, WITH SUFFICIENT ADDED WATER TO INDUCE IN THE MIXTURE THE DESIRED PLASTICITY. 